Vat dyestuffs of the anthraquinone series



Patented June 3, 1941 "U NITE DsTATEs PATENT OFFlCE OF THE. ANTHR'AQU INO'N E SERIES Hans Schlichenmaier and Ludwig Wilhelm Berlin, Frankfort on the Main,

and Erich Berthold, Lu'dwigshafen-on-the-Rhine, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Applicationv February 4, '1939, Se-

rial No. 1,254,538. In Germany February 9,

8 Claims.

The present invention relates to new vat dyestuffs of the anthraquinone series.

We have found that anthraquinone azoles corresponding to the general formula V smog;

n being an integer up to 2, are valuable vat dye stuffs.

A suitable method for preparing the said dyestuffs consists in causing an aminoanthraquinone azole corresponding to the general formula wherein R and X have the meanings mentioned above and which contains in one of the alpha positions of the anthraquinonyl radicle an amino group, to react in the usual manner with an omega-trifluormethylarylcarboxylic acid halide, for instance by heating the reaction components in a solvent of high boiling point such as nitrobenzene, trichlorbenzene and the like. v

The new dyestuffs are distinguished by'their valuable tinctorial properties, especially by their clear tint and their excellent fastness to light.

The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples. The parts are by weight.

1. 20 parts of 1-4-diamino-2-anthraquinonyl- 2-3'-anthraquinone-oxazole (prepared as indicated in Example 1 of German Patent No. 623; 028) in 400 parts of nitrobenzene are heated, within the course of 4 hours to 190 C.-200 0, together with 20 parts of meta-w-trifiuoromethylbenzoylfluoride and the whole is kept at this temperature until hydrogen fluoride is no longer evolved and no parent material can be detected. The dyestufi which separates in the form of blue needles is isolated by filtering with suction, while hot; it is then washed until free from nitrobenzene and dried. The yield is very good.

The 1-amino-4-meta-wtrifluoromethy1ben zoylamino 2 anthraquinonyl-2-3-anthraquinone-oxazole thus obtained is a blue-red crystal line powder having a metallic luster; it dissolves in concentrated sulfuric acid to a yellow-olive solution and dyes vegetable fiber, in a violet vat,

intense, clear, reddish-blue tints which are very fast to chlorine and to light.

If para-w-trifluoromethylbenzoyl fluoride is used, the corresponding para-w-trifluoromethylbenzoyl derivative having similar properties is obtained in the same manner.

'2. 20 parts of 1-4 diamino-2-anthraquinonyl- 2-3 -anthraquinone-thiazole (obtainable as indicated in Example 11 of German Patent No.

623,028) in 300 parts of nitrobenzene are treated, together with 18 parts of metaw-trifiuoromethylbenzoyl fluoride, as indicated in Example 1. The 1-amino-4-meta-w-trifluoromethylbenzoylamino 2 anthraquinonyl-2-3'-anthraqui- #none-thiazole, which is thus obtained with a practically quantitative yield in the form of bluered needles having a metallic luster, dissolves in concentrated sulfuric acid to an olive-green solution and dyes cotton, in a violet vat, clear, in-

'tense, greenish-blue tints having very good prop- '2 -3 -anthraquinone -oxazole erties of fastness.

When the ortho-w-trifiuoromethylbenzoyl fluoride is used instead of the meta-derivative, a dyestuff having similar properties is obtained.

3. 50 parts of 1-4-'diamino-2-anthraquinonyl- 1'(N) 2'(0) anthraquinone oxazole obtainable as indicated inv Example 5 of German Patent 623,028) in 1000 parts of nitrobenzene are slowly heated to 200 C., together with 50 parts of metawtrifluoromethylbenzoyl fluoride and 0.5 part of pyridine and the whole is kept at this temperature until the blue crystals of the 4-meta-w-trifiuoromethylbenzoylamino-derivative are formed. The whole is filtered with suction, while hot, and the residue is worked up as described above. The dyestufl' dissolves in concentrated sulfuric acid to a yellow solution and dyes vegetable fiber,

in a red-violet vat, reddish-blue tints.

4. 25 parts of 1-5-diamino-2eanthraquinonyl- (prepared as indicated in Example 4 of German Patent No. 623,028) in 500 parts of nitrobenzene are heated at 180 C.-200 0., together with 20'parts'of meta-w-trifluoromethylbenzoyl fluoride, until hydrogen fluoride is no longer evolved and no parent material can be detected. After working up as described above, the dyestufi is obtained, with a good yield, in the form of bluered crystals having a metallic luster which dissolve in concentrated sulfuric acid to a yellow solution and dye cotton, in a dark violet vat, clear, intense ruby-red tints having very good properties of fastness.

Dyestuffs having similar properties are obtained from an w-trifiuorornethylbenzoyl halide and 1 diamino 2 anthraquinonyl-1(N) 2' (O) -anthraquinone-oxazole.

5. 25 parts of l-4-diamino-2-anthraquinonyl- 1 (S) -2 (N) -anthraquinone-thiazole (obtainable for example by condensing l-aminol-nitroanthraquinone-Z-carboxylic acid chloride with 1-chlor-2-amino-anthraquinone, heating the 1 amino 4 -nitroanthraquinone-2-carbonyl-2'- amino-1'-chloranthraquinone thus obtained with sodium sulfide and sulfur in pyridine to form l.4-diaminoanthraquinone-2-carbonyl-2'-aminol-mercapto-anthraquinone whereupon the ring closure is efiected by heating it in concentrated sulfuric acid at about 100 C.) in 400 parts of nitrobenzene are heated at 180 C'.-200 C. together with 20 parts of meta-w-trifluoromethylbenzoyl fluoride, until the formation of the dye- 1. Vat dyestuffs of the anthraquinone series corresponding to the formula O wherein R stands for the radical of an unsubstituted anthraquinone, X for a member selected from the group consisting of O and -S, the linkages from N and X to R. leading to neighboring positions of R, and containing in one of the alpha positions of the aminoanthraquinonyl radical the group n being an integer up to 2, the other positions being occupied by hydrogen.

2. Vat dyestuffs of the anthraquinone series corresponding to the formula 0 N112 II I N c R X wherein R stands for the radical of an unsubstituted anthraquinone, X for a member selected from the group consisting of -O and S-.

the linkages from N and X to R leading to neighboring positions of R, and containing in one of the alpha positions of the amino-anthraquinonyl radical the group the other positions being occupied by hydrogen. 3. Vat dyestuffs of the anthraquinone series corresponding to the formula wherein R stands for the radical of an unsubstituted anthraquinone, X for a member selected from the group consisting of O- and --S, the linkages. from N and X to R leading to neighboring positions of R, and containing in one of the alpha positions of the amino-anthraquinonyl radical the group the other positions being occupied by hydrogen. 4. The Vat dyestufis of the anthraquinone series corresponding to the formula wherein X stands for a member selected from the group consisting of -O-- and S and n for an integer up to 2, the other positions being occupied by hydrogen.

5. The vat dyestuff of the anthraquinone series corresponding tothe formula wherein X stands for a member selected from the class consisting. of -+O'' and S-, the other positions being occupied by hydrogen.

6. The vat dyestuff of the formula which dyes from a, violet vat vegetable fibers 8. The vat dyestuff of the formula clear reddish blue shades of very good fastnes's to chlorine, washing and light.

'7. The vat dyestufi of the formula 0 0 NH? H 11 H (H) N 2 /N 0 O\S 10 o\ 0 I o i Y which dyes from a redviolet vat vegetable fibers blue shades of very good fastness to chlorine,

which dyes from a. violet vat vegetaA-me fibers Washing and light- HANS SOHLICHENMAJER.

clear greenish blue shades of very good fastness 20 to chlorine, washing and light. LUDWTG W M R IN- ERICH BERTHOLD. 

